CN102076636A - Process to make olefins from oxy-compound - Google Patents
Process to make olefins from oxy-compound Download PDFInfo
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- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B01J29/00—Catalysts comprising molecular sieves
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
- C07C1/322—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom the hetero-atom being a sulfur atom
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/36—Steaming
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
The present invention relates to a process to make light olefins, in a combined XTO-OC process, from an oxygen-containing, halogenide-containing or sulphur-containing organic feedstock comprising : a0)providing a first portion and a second portion of said oxygen-containing, halogenide-containing or sulphur-containing organic feedstock, a)providing a catalyst comprising zeolitic molecular sieves containing at least 10 membered ring pore openings or larger in their microporous structure; b)providing an XTO reaction zone, an OC reaction zone and a catalyst regeneration zone, said catalyst circulating in the three zones, such that at least a portion of the regenerated catalyst is passed to the OC reaction zone, at least a portion of the catalyst in the OC reaction zone is passed to the XTO reaction zone and at least a portion of the catalyst in the XTO reaction zone is passed to the regeneration zone; c)contacting the first portion of said oxygen-containing, halogenide- containing or sulphur-containing organic feedstock in the XTO reactor with the catalyst at conditions effective to convert at least a portion of the feedstock to form a XTO reactor effluent comprising light olefins and a heavy hydrocarbon fraction; d)separating said light olefins from said heavy hydrocarbon fraction; e)contacting said heavy hydrocarbon fraction and the second portion of said oxygen-containing, halogenide-containing or sulphur-containing organic feedstock in the OC reactor with the catalyst at conditions effective to convert at least a portion of said heavy hydrocarbon fraction and oxygen-containing, halogenide-containing or sulphur-containing organic feedstock to light olefins.
Description
Technical field
The present invention relates to by the heteroatoms organism make the method for alkene and more properly with XTO (organism the is converted into alkene) method of OC (conversion of olefines) method combination, it at least a portion that comprises that catalyst regeneration zones and feasible at least a portion through regenerated catalyst pass to the catalyzer in OC reaction zone and the described OC reaction zone passes to the XTO reaction zone.The part of described organism (compound that contains X) is delivered to described OC reaction zone and remainder is delivered to described XTO reaction zone.
The limited supply of crude oil and the cost that increases have day by day impelled seeks the alternative method of making hydrocarbon product.A kind of such method is that the organic compound with the organic compound of oxygen containing organic compound (for example methyl alcohol), halide or sulfur-bearing is converted into hydrocarbon and particularly light olefin (light olefin refers to C
2～C
4Alkene) or gasoline and aromatic hydrocarbons (aromatic substance, aromatics).In this application, the described organic compound that contains oxygen, halide or sulfur-bearing is also referred to as " X ".In this application, the organic compound of the organic compound of described oxygen containing organic compound (being also referred to as oxygenatedchemicals), halide or sulfur-bearing is called the XTO method to the conversion of hydrocarbon and particularly light olefin.To the concern of XTO method based on the following fact: raw material particularly methyl alcohol can be obtained by making synthetic gas (described synthetic gas is handled then to make methyl alcohol) by coal, hydrocarbon residue (residu), biomass, organic waste or Sweet natural gas.The XTO method can make up to improve the output of alkene with OC (conversion of olefines method) method.The XTO method produces light olefin for example ethene and propylene and heavy hydrocarbon for example more than the butylene.These heavy hydrocarbons in the OC method cracking mainly to obtain ethene and propylene.Under the situation of methyl alcohol (methanol conversion is an alkene) method, the XTO method is also referred to as MTO.
Background technology
It is the method for alkene that US7132581 relates to oxygenate, and it comprises that the catalyzer to using carries out pretreated step in conversion reaction.With low fresh of carbon content or through the aldehyde pre-treatment of regenerated metalloaluminophosphate molecular sieve.Described aldehyde in the pore structure of described molecular sieve, form the hydrocarbon promotor and with this contain described promotor to be used for oxygenate through pretreated molecular sieve be olefin product.
It is the method for alkene that US7057083 relates to oxygenate, and it comprises uses the C4-C7 compositions of olefines that contains one or more C4-C7 alkene that the molecular sieve that uses in conversion reaction is carried out pretreated step.With low fresh of carbon content or through the regenerated molecular sieve contact with described compositions of olefines or with described compositions of olefines pre-treatment form in pore structure at described molecular sieve the hydrocarbon promotor and with this contain described promotor be used for oxygenate is light-weight olefin product more through pretreated molecular sieve.
US6844476 has described the heavy olefin conversion that will be present in the product logistics of leaving first reaction zone be light olefin with catalyzer on carbonaceous sediment and from the described product logistics of leaving first reaction zone, do not separate the method for described heavy olefins.Described method comprises: produce the product logistics of leaving described first reaction zone, the described product logistics of leaving first reaction zone comprises described heavy olefins; The described product logistics of leaving first reaction zone delivered to second reaction zone and from the described product logistics of leaving first reaction zone, do not separate described heavy olefins; With the described product logistics of leaving first reaction zone is contacted under the condition that forms described light olefin effectively with catalyzer, described contact causes at least a portion of described catalyzer forming described carbonaceous sediment.
US20060161035 has described by the oxygenate using following combination to improve in fact the to use difunctional oxygenate conversion catalyst average propylene circulation productive rate as propylene (OTP) method:
1) in catalytic OTP reaction step, the moving-burden bed reactor technology generation is for the bed technology of prior art;
2) independent heavy olefins change step, its use moving bed technique and the temperature in of at least 15 ℃ of the top temperature height that in than described OTP reactions steps, use under operate;
3) the C2 olefin recycle is to described OTP reactions steps; With
4) 700 hours or catalyst runs cycling time still less.These measures make the accumulation of the deposits of coke on the described catalyzer remain such level: this level does not reduce dual-function catalyst activity, oxygenate and propylene selectivity basically, thus make each round-robin average propylene circulation productive rate can keep near or be essentially the level of circulation beginning.
US5914433 relates to the method for being made light olefin by oxygen-containing compound material, and described light olefin comprises that each molecule has the alkene of 2～4 carbon atoms.Described method comprises described oxygen-containing compound material is passed to the oxygenate district of containing the metallic aluminium phosphate catalyst to make light olefin stream.From described light olefin stream fractionation propylene stream and/or blended butylene and with butylene and heavy component cracking to improve the productive rate of ethene and propylene product.Light olefin product and butylene and heavy component cracked in the riser cracking district or the independent zone of cracking is this to be combined as the handiness that described method provides the equilibrium-limited that overcomes described aluminate or phosphate catalyzer.In addition, this invention is provided at the advantage of the catalyst stability of the catalyst life that prolongs in the oxygenate district and Geng Gao.In described method, the effluent of the described riser cracking district or the described independent zone of cracking is delivered to described oxygenate district.
Have now found that by oxygenatedchemicals and make the particularly more efficient methods of propylene of light olefin.The present invention relates to comprise the method in following three districts: contain the XTO reaction zone of catalyzer, wherein " X " (for example oxygenatedchemicals) mainly is converted into light olefin; The OC reaction zone that contains substantially the same catalyzer, wherein more the alkene of heavy and optional ethylene cracker are other light olefin; Wherein make district's (catalyst regeneration zones is also referred to as the breeding blanket) of the catalyst regeneration that in other two districts, uses.The present invention relates to (in the XTO reaction zone) is the method for alkene with oxygenate on based on the catalyzer of zeolite, it comprises the steps: described catalyzer based on zeolite at first is used in and uses in the conversion reaction of olefin feedstock basically (OC reaction zone), and described raw material contains one or more C
2-C
12Alkene; With on described molecular sieve, form for example 0.1 weight % or more coke shape settling.The sedimental main effect of this hydrocarbon is the selectivity inactivation of non-selective acid sites.This of described molecular sieve and olefin feedstock contacts and can carry out under the situation that has or do not exist water and oxygenated compound.In most preferred embodiments, this contact is carried out under the situation that does not have water.Find, the catalyzer that has at the catalyst performance of the remarkable improvement of the MTO of XTO reaction zone reaction will be provided based on the conversion (as pre-treatment) that the catalyzer of zeolite at first is used for olefin feedstock.Do not wish to be bound by any theory, think that this effect is the selectivity poisoning of the non-selective acid sites of outer surface, described non-selective acid sites typically is the reason that causes side reaction, causes the enhancing of paraffinic hydrocarbons and aromatic hydrocarbons to form.In the present invention, we talk about wherein sedimentary coke and do not have the catalyzer through the pre-inactivation of selectivity as the catalytic activity in the situation of the coke promotor on the SAPO section bar material.
For another advantage based on the use compositions of olefines of the present invention that at first uses of the catalyzer of zeolite is that this provides the approach that the by product do not expected of oxygenatedchemicals in the overall conversion of alkene reduced.Typically, than heavy olefins C for example
4-C
7The by product that alkene is considered to not expect is because the value of those alkene significantly is lower than ethene and propylene.Therefore, oxygenate can be used for strengthening ethene and the propylene product of selectivity of catalyst so that more expectation to be provided for the by product of the reaction process of alkene.
Advantage of the present invention:
-in each operational zone, under top condition, react
-by described catalyzer at first being used for the optimum catalyst selectivity of cracking of olefins
-heat integration preferably (heat integration) between the different reactor district
Because the overall yield of the higher light olefin that lower paraffinic hydrocarbons and aromatic hydrocarbons form.
Preferably, the catalyzer in these three districts is in fluidized.This allows catalyzer easily is transported to other district from a district.
In the independent district (XTO reaction zone) different, carry out the conversion of X with the conversion (in the OC reaction zone) of ethene or C4-C7 hydrocarbon.This allows and optimizes each reaction conditions respectively.Therefore the conversion of X is the conversion of strong heat release, and is preferably in the fluidized-bed that has basic uniform temperature in the whole catalyst bed and carries out, and wherein temperature is by following adjusting: be infused in the raw material (cold raw material is used as low-temperature receiver) under the temperature that is lower than temperature of reaction; Perhaps make described catalyzer cooling by in heat exchanger, rising vapour by means of catalyst cooler.On the contrary, the C4-C7 conversion of olefines is the reaction of strong endothermic.The heat of reaction can provide by following: make raw material overheated, make that the temperature out of reactor is enough high to obtain sufficiently high feedstock conversion.The heat of reaction also can by at enough height so that the high catalyst cycle rate under the temperature of feedstock conversion provide.This can be easily has that catalyzer at reactor bottom (inlet) injects and is carrying out at the fluidized-bed reactor of the catalyst separating of reactor head (outlet).Enough Re catalyzer can be from wherein by making the coke incendiary revivifier that is deposited on the catalyzer in a controlled manner with air.In order to make rate of combustion the highest and make temperature of combustion minimum, add combustion improver well known by persons skilled in the art.Described combustion improver is made up of the platinum on the alumina supporter.During X or C4-C7 conversion of olefines, do not deposit under the situation of enough coke, can in revivifier, inject extra fuel and heat more catalyzer, make more heat can flow to the C4-C7 zone of transformation so that heat to be provided.The example of extra fuel is Sweet natural gas, LPG, heating oil or synthetic gas.Especially, the synthetic gas that is rich in CO is suitable.This synthetic gas that is rich in CO is can easily obtain as for example purge flow in methanol sythesis reactor loop in the synthetic factory of methyl alcohol.
Another source of thermocatalyst is the XTO reaction zone, because the conversion of X is strong heat release.Leave the temperature of the catalyzer in XTO district should be at least than for obtaining enough conversions at the needed temperature height in the exit in C4-C7 cracking of olefins district.The conversion of C4-C7 alkene on the thermocatalyst of carrying from the XTO district is a kind of catalyst cooler of the XTO of being used for reaction zone.
Although preferably contain compound and the C4-C7 conversion of olefines of X respectively in XTO and OC reaction zone as the above in each independent reaction zone, highly Xi Re cracking of olefins can be undertaken by at least a portion of the compound of the described X of containing and described C4-C7 alkene are made up in described OC reaction zone.The amount of the compound that contains X that is transformed should reduce because the temperature loss that the C4-C7 cracking of olefins of heat absorption causes.This amount should advantageously be no more than the value when the conversion of this combination becomes heat release.
Summary of the invention
The present invention relates to comprise by the method for the organic raw material that contains oxygen, halide or sulfur-bearing with the XTO-OC method manufacturing light olefin of combination:
A0) provide the described organic raw material that contains oxygen, halide or sulfur-bearing of first part and second section,
A) provide the catalyzer that comprises zeolite molecular sieve, described zeolite molecular sieve contains at least 10 yuan of annular distance openings or bigger hole opening in its microvoid structure;
B) provide XTO reaction zone, OC reaction zone and catalyst regeneration zones, described catalyzer circulates in described three districts, feasible at least a portion through the regenerated catalyzer passes to described OC reaction zone, and at least a portion that at least a portion of the catalyzer in the described OC reaction zone passes to the catalyzer in described XTO reaction zone and the described XTO reaction zone passes to described breeding blanket;
C) make the described organic raw material that contains oxygen, halide or sulfur-bearing of described first part in described XTO reactor, under the condition of at least a portion that transforms described raw material effectively, contact the XTO reactor effluent that comprises light olefin and heavy hydrocarbon fractions with formation with described catalyzer;
D) described light olefin is separated with described heavy hydrocarbon fractions;
E) the described organic raw material that contains oxygen, halide or sulfur-bearing that makes described heavy hydrocarbon fractions and described second section contacts under the condition that effectively described heavy hydrocarbon fractions and at least a portion of containing the organic raw material of oxygen, halide or sulfur-bearing is converted into light olefin with described catalyzer in described OC reactor.
Advantageously, the amount of " X " of the described second section in the OC raw material makes described OC reactor work near the boundary of heat absorption and heat release condition.For example, " X " ratio in the OC raw material of described second section is about 15～about 30 weight % and advantageously is about 20～30%.
Described XTO reaction zone can be made of one or more reactors.
Described OC reaction zone can be made of one or more reactors.
Described breeding blanket can be made of one or more reactors.
Described XTO reaction zone can be arranged in identical reactor with described OC reaction zone.
Described catalyzer can be the mixture of two or more catalyzer and optional binding agent.
Essential feature of the present invention is to use identical catalyzer in described XTO and OC reaction zone.
Be desirably in and have 100% organic compound conversion basically in the described XTO reactor.This transformation efficiency is regulated by the optimization of the regeneration frequency of duration of contact, temperature of reaction and catalyzer.
In embodiment, the WHSV of X is about 0.5～about 4h in the described XTO reaction zone
-1, advantageously be about 1～about 2 and described OC reaction zone in WHSV be about 5～about 12h
-1, advantageously be about 8～about 12.
Advantageously, must contain at least 0.1% carbon from described OC district and the catalyzer that flows to the XTO section.
About the effluent of described XTO method, " light olefin " refers to that ethene and propylene and " heavy hydrocarbon fractions " are defined as in this article and contains the cut of molecular weight greater than the hydrocarbon of propane, and it refers to has 4 or more a plurality of carbon atom and note is made C
4 +Hydrocarbon.Described C
4 +Cut also can contain the compound that azeotropic contains X, for example methyl alcohol and other oxygenatedchemicals.
According to embodiment, described catalyzer is the P-modified zeolite.These phosphorus modified molecular sieves of the present invention are based on initial Si/Al and prepare than MFI, the MOR, MEL, clinoptilolite or the FER crystalline aluminosilicate molecular sieve that advantageously are 4～500.These P-modified zeolites also can obtain based on having the cheap crystalline aluminosilicate of low Si/Al than (being lower than 30).This provides lower final catalyzer cost.
The catalyzer of being made by the P-modified zeolite can be described P-modified zeolite self, and perhaps it can be by being formulated as the P-modified zeolite of catalyzer with other combination of materials that extra hardness or catalytic activity are provided to the catalyst product of finishing.
According to first embodiment, described P-modified zeolite is by comprising the method manufacturing of following order:
-at the H of MFI, MEL, FER, MOR, clinoptilolite
+Or NH
4 +Select zeolite (advantageously have 4～500 Si/Al than) in the form;
-introduce P introducing effectively under the condition of at least 0.05 weight %P advantageously;
If-there is liquid, with solid and liquid separation;
-optional washing step, perhaps Ren Xuan drying step, perhaps Ren Xuan drying step and washing step afterwards;
-calcining step.
Randomly, the method for making described P-modified zeolite comprises decatize and leaching (leaching, leach) step.Described method is to leach after the decatize.Those skilled in the art know usually, and the steam treatment of zeolite produces to be left zeolite framework and be present in the hole of zeolite as aluminum oxide and the aluminium outside the hole.Dealuminzation and this term that this conversion is called zeolite will use in the text.Handle the dissolving that causes skeleton external oxidation aluminium through the zeolite of decatize with acidic solution.This conversion is called leaching and this term will use in the text.Then zeolite is separated, advantageously by filtration, and randomly washing.Can between filtration and washing step, design drying step.Solution after the washing can evaporate or for example by filter with solids constituent from.P can be by any way or for example according to US 3,911, and 041, US 5,573,990 and US6, the method described in 797,851 is introduced.Liquid separate with solid advantageously by filter under 0～90 ℃ the temperature, centrifugal under 0～90 ℃ temperature, evaporate or be equal to means and carry out.Randomly, described zeolite can be dry before the after separating washing.Advantageously, described drying was advantageously carried out 1～10 hour under 40～600 ℃ temperature.This drying can be carried out at static conditions or in air-flow.Can use air, nitrogen or any rare gas element.Washing step can use a part of cold water (＜40 ℃) or hot water (＞40 ℃ but＜90 ℃) to carry out during filtering (separating step), perhaps can make the described solid experience aqueous solution (1kg solid/4 premium on currency solution) and under refluxad handled 0.5～10 hour, evaporate subsequently or filter.Last calcining step is advantageously carrying out under static conditions or in air-flow under 400～700 ℃ the temperature.Can use air, nitrogen or any rare gas element.
Can be P-modified zeolite itself or its by the catalyzer of P-modified zeolite manufacturing can be by being formulated as the P-modified zeolite of catalyzer with other combination of materials that extra hardness or catalytic activity are provided to the catalyst product of finishing.
According to the embodiment of the present invention, described phosphorus-modified zeolite is by comprising the method manufacturing of following order:
-at the H of MFI, MEL, FER, MOR, clinoptilolite
+Or NH
4 +Select zeolite (advantageously having 4～500 Si/Al ratio, is 4～30) in the form in specific implementations;
-decatize 0.01～200 hour under 400～870 ℃ temperature;
-under the condition of from described zeolite, removing signal portion Al effectively, leach with aqueous acid solution;
-use the aqueous solution that contains the P source to introduce P introducing effectively under the condition of at least 0.05 weight %P advantageously;
-with solid and liquid separation;
-optional washing step, or optional drying step, or optional drying step and washing step afterwards;
-calcining step.
Randomly, between steaming step and leaching step, there is intermediate steps, for example, for instance, contacts and drying with SiO 2 powder.
According to second embodiment, the catalyst complex of the catalyzer of the XTO-OC method of described combination for making by the method that may further comprise the steps:
A) select to have the molecular sieve in the hole of 10 yuan or more polynary ring
B) described molecular sieve is contacted with the metal silicate that comprises at least a alkaline-earth metal, make described mixture comprise the silicate of at least 0.1 weight %.
Preferably described molecular sieve is contacted with described metal silicate by one of following two kinds of methods:
-during the preparation of catalysts step,, form the precursor that is ready to use in the described preparation steps by with described molecular sieve and described metal silicate mechanical blending;
-the molecular sieve that will prepare in advance and metal silicate original position physical blending in XTO and/or OC reaction medium of preparing in advance.
The optional tabulation down freely of described molecular sieve: MFI, MOR, MEL, clinoptilolite, FER, FAU, MWW, BETA, ZSM-21, ZSM-22, ZSM-23, ZSM-42, ZSM-57, LTL or its mixture.Preferably, described MFI is the ZSM-5 zeolite.More preferably, described molecular screening is from MFI, MOR, MEL, clinoptilolite, FER or its mixture.In another embodiment, described molecular sieve preferably obtains under the situation of directly not adding template.
Described molecular sieve and/or contain the described catalyst complex of described molecular sieve and metal silicate can be by calcining, pulverize (reduction, reduction) or decatize come aftertreatment.Using under the situation of zeolite as molecular sieve component, can with the metal metasilicate salt blend before, introduce phosphorus simultaneously or afterwards.
The composition of described catalyst complex comprises:
The molecular sieve in the hole of at least 10 weight % with 10 yuan or more polynary ring
At least a metal silicate that comprises at least a alkaline-earth metal makes described catalyst complex comprise the silicate of at least 0.1 weight %
Optional metal phosphate
Optional body material
Optional binding agent.
According to the 3rd embodiment, alkaline-earth metal or the rare earth metal-P-modified molecular screen (M-P-modified molecular screen) of the catalyzer of the XTO-OC method of described combination for making by the method that comprises the steps:
A) select at least a molecular sieve, described molecular screening is from one of following:
-contain the P-modified molecular screen of at least 0.3 weight %P
-before the step b) or during introduce the molecular sieve of at least 0.3 weight %P with the P modification
B) described molecular sieve is contacted to introduce described alkaline-earth metal or the rare earth metal M of 0.05 weight % at least with the compound (compound that contains M) of alkaline including earth metal or rare earth metal.
Randomly, described molecular sieve can carry out simultaneously with described the contacting of compound that contains P-compound and the described M of containing.
The introducing of described alkaline-earth metal or rare earth metal (M) is to contact by the solution that makes described molecular sieve and one or more contain the compound of M to carry out.Described solution can contain than alkaline-earth metal that exists in final M-P-modified molecular screen or high alkaline-earth metal or the rare earth metal concentration of rare earth metal concentration.
With phosphorus modified molecular sieves is that itself is known.This modification is undertaken by following: handle molecular sieve with P-compound in water or non-aqueous media, organic P-compound of chemical vapour deposition or dipping.Described catalyzer can with binding agent or not with the binding agent preformulation.The preferred P-compound that the typical case is used for this purpose can be selected from phosphoric acid, NH
4H
2PO
4Or (NH
4)
2HPO
4
The described compound that contains M is optional from organic compound, salt, oxyhydroxide and oxide compound.These compounds also can contain phosphorus.Necessary is, before making these compounds and described molecular sieve contact, make these compounds with solubilisate (solubilising, solubilized) form existence, perhaps these compounds exist by formation solution when contacting with described molecular sieve.
Final mol ratio M/P in the described M-P-molecular sieve is preferably less than 1.
The optional tabulation down freely of described molecular sieve: MFI, MOR, MEL, clinoptilolite, FER, FAU, MWW, BETA, MCM-41, ZSM-21, ZSM-22, ZSM-23, ZSM-42, ZSM-57, LTL or its mixture.More preferably, described molecular screening is from MFI, MOR, MEL, clinoptilolite, FER or its mixture.Under the situation of MFI, described molecular sieve is preferably the ZSM-5 zeolite.In another embodiment, described molecular sieve preferably obtains under the situation of directly not adding template.
Preferably, the average cell size of described molecular sieve is 0.5nm at least.
Described molecular sieve with can calcining, decatize, ion-exchange before M and the P modification, handle with acidic solution, perhaps it can cause other processing of dealuminzation.The dealuminzation of described molecular sieve can carry out simultaneously with described phosphorus modification.
Embodiment
About first embodiment of the present invention, and selected zeolite, advantageously, it is the crystalline aluminosilicate of MFI class or MEL class.The example of MFI silicate is ZSM-5.The example of MEL zeolite is the ZSM-11 that knows in this area.Other example is by International Zeolite Association (Atlas of ZeoliteStructure Types, 1987, Butterworths) description.
Crystalline silicate is based on the XO shared connected to one another by oxonium ion
4The microporous crystalline inorganic polymer of the skeleton of tetrahedron (tetrahydra), wherein X can be trivalent (for example Al, B ...) or tetravalence (for example Ge, Si ...).The crystalline structure of crystalline silicate is limited by the particular order that the network of tetrahedron element wherein links together.The size of crystalline silicate hole opening is by the quantity that forms required tetrahedron element in hole or Sauerstoffatom and be present in cationic character decision in the described hole.They have the unique combination of following character: high internal surface area; Even hole with one or more discrete size; The ion interchangeability; Good thermostability; With the ability that is adsorbed with organic compounds.Because the hole of these crystalline aluminosilicates is similar with many organic molecules that reality is concerned about dimensionally, entering and discharging of their control reactants and product causes the specific selectivity in the catalyzed reaction.Crystalline aluminosilicate with MFI structure has the bidirectional crossed pore system that has following aperture: along the straight channel of [010]: 0.53-0.56nm with along the sinusoidal passage of [100]: 0.51-0.55nm.Crystalline aluminosilicate with MEL structure has bidirectional crossed straight hole system, wherein has the aperture of 0.53-0.54nm along the straight channel of [100].
Advantageously, selected MFI, MEL, FER, MOR, clinoptilolite (the perhaps H of MFI, MEL, FER, MOR, clinoptilolite
+Or NH
4 +Form) has 100 or lower initial atomic ratio Si/Al and in embodiment, have the initial atomic ratio Si/Al of 4-30.To H
+Or NH
4 +The conversion of form itself be known and be described in US 3911041 and US 5573990 in.
In the steam treatment step, temperature is preferably 420 ℃～870 ℃, more preferably 480～760 ℃.Pressure is preferably normal atmosphere and water partial pressure can be 13～100kPa.Steam atmosphere preferably contains 5～100 volume % steam and 0～95 volume % rare gas element, preferred nitrogen.Described steam treatment was preferably carried out 0.01～200 hour, and advantageously 0.05～200 hour, more preferably 0.05～50 hour.Described steam treatment is tending towards by forming the amount that aluminum oxide reduces tetrahedral aluminium in the crystalline silicate framework.
Described leaching can be used organic acid, and for example citric acid, formic acid, oxalic acid, tartrate, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, toxilic acid, phthalic acid, m-phthalic acid, fumaric acid, complexon I, HEDTA, ethylenediamine tetraacetic acid (EDTA), trichoroacetic acid(TCA), trifluoroacetic acid or the salt (for example sodium salt) of such acid or the mixture of two or more such acid or salt carry out.Other mineral acid can comprise mineral acid for example nitric acid, hydrochloric acid, methane sulfuric acid, phosphoric acid, phosphonic acids, sulfuric acid or the salt (for example sodium salt or ammonium salt) of such acid or the mixture of two or more such acid or salt.
Advantageously, final P content is at least 0.05 weight % and be preferably 0.3～7 weight %.Advantageously, with respect to parent zeolite MFI, MEL, FER, MOR and clinoptilolite, at least 10% Al extracts from described zeolite and removes by leaching.
Then, described zeolite is separated with washing soln or be dried and do not separate with washing soln.Described separation is advantageously undertaken by filtration.Calcine described zeolite then, for example calcined 2～10 hours down at 400 ℃.
If the washing procedure by the P concentration in the aqueous acid solution that contains the P source, drying conditions and existence is regulated residual P content.Can between filtration and washing step, design drying step.
But described P-modified zeolite self is as catalyzer.In another embodiment, it can be by being formulated as catalyzer with extra hardness or other combination of materials of catalytic activity are provided to the catalyst product of finishing.Can be various inertia or catalytically active material with the material of described P-modified zeolite blend, perhaps various binder materials.These materials comprise composition for example kaolin and other clay, various forms of rare earth metal, phosphoric acid salt, aluminum oxide or alumina sol, titanium dioxide, zirconium white, quartz, silicon-dioxide or silicon dioxide gel, and composition thereof.These components are being effective aspect the intensity of the catalyzer that catalyzer densification and raising are prepared.Described catalyzer can be formulated as spray-dired particle.The amount of the P modified zeolite that contains in the final catalyst product is 10～90 weight % of total catalyst, is preferably 20～70 weight % of total catalyst.
About second embodiment of the present invention, the molecular sieve that can use in the present invention is preferably zeolite, for example crystalline silicate, more properly aluminosilicate.Crystalline silicate is for based on by sharing oxonium ion XO connected to one another
4The microporous crystalline inorganic polymer of tetrahedral skeleton, wherein X can be trivalent (for example Al, B ...) or tetravalence (for example Ge, Si ...).The crystalline structure of crystalline silicate is limited by the particular order that the network of tetrahedron element wherein links together.The size of crystalline silicate hole opening is by the quantity that forms required tetrahedron element in hole or Sauerstoffatom and be present in cationic character decision in the described hole.They have the unique combination of following character: high surface-area; Even hole with one or more discrete size; The ion interchangeability; Good thermostability; With the ability that is adsorbed with organic compounds.Because the hole of these crystalline aluminosilicates is similar with many organic molecules that reality is concerned about dimensionally, entering and discharging of their control reactants and product causes the specific selectivity in the catalyzed reaction.
Selected molecular sieve can be by means of the seed technology manufacturing, but advantageously they are made under the situation of template not having.Yet seed self can use the template manufacturing, this means in the case, and described molecular sieve is to make under the situation of directly not adding template.Preferably, the molecular sieve that uses among the present invention is made under the situation of directly not adding template.
The molecular sieve that selection is used for the object of the invention has the hole of 10 yuan or more polynary ring size.Can design to use and have by 10,12 or the molecular sieve of the more polynary annular distance that constitutes.
Selected molecular sieve according to the present invention has at least 0.5, preferred 0.5～10, more preferably 0.5～5 and the average cell size of most preferably at least 0.5～0.9nm.
Selected molecular sieve has at least 4 and be not more than 500 initial atomic ratio Si/Al.Described Si/Al atomic ratio is by chemical analysis, for example uses XRF and/or NMR to record.It only comprises those Al as the part of the skeleton structure of described molecular sieve.
About selected molecular sieve, advantageously, according to International Zeolite Association (Atlas of ZeoliteStructure Types, 1987, Butterworths), it is selected from MFI, MOR, MEL, clinoptilolite, FER, FAU, MWW, BETA, ZSM-21, ZSM-22, ZSM-23, ZSM-42, ZSM-57, LTL or its mixture.Preferably, it is selected from MFI, MOR, MEL, clinoptilolite, FER or its mixture.More preferably, described MFI is the ZSM-5 zeolite.
In another embodiment, the described molecular sieve that is selected from MFI, MOR, MEL, clinoptilolite, FER or its mixture preferably obtains under the situation of directly not adding template.
Catalyst complex as described in described molecular sieve can be used to form as institute's synthetic.Before the described catalyst complex of preparation, described molecular sieve can further be handled, and comprises decatize, leaching (for example, acidleach is got), washing, drying, calcining, dipping and ion-exchange step.In addition or alternatively, these steps also can be carried out after the preparation of described catalyst complex.
In the specific embodiment of the present invention, described molecular sieve can be before the introducing of metal silicate or modification afterwards.Preferably, described molecular sieve had carried out the modification of a certain form before metal silicate is introduced.Modification refers to that in this article molecular sieve can carry out the ion-exchange of decatize, leaching (for example, acidleach is got), washing, drying, calcining, dipping or a certain form.This means, can substitute the cationic at least a portion that comprises at first in the described crystalline structure with various other positively charged ions according to techniques well known in the art.Place of cation can be hydrogen, ammonium or other metallic cation, comprises so cationic mixture.
Then, selected molecular sieve is mixed with catalyst complex to comprise at least 10 weight % molecular sieve and at least a metal silicate that comprises at least a alkaline-earth metal as described herein, makes described mixture comprise the silicate of at least 0.1 weight %.
At least a at least a alkaline-earth metal, the preferred Ca of comprising of the metal silicate that comprises in the described catalyst complex.Water insoluble and the alkaline-earth metal ions of metal silicate particularly calcium is polyvalent and has big radius under hydration status.Therefore, be not wishing to be bound by theory, think because for alkaline-earth metal ions in the micropore that infiltrates molecular sieve structure must lose its many firm coordinate water moleculess, therefore the ion exchange reaction with described molecular sieve takes place very lentamente.As a result, described alkaline-earth metal ions only makes the acid sites that is positioned on the molecular sieve outer surface expose, and improves selectivity of catalyst thus.
In addition, be not wishing to be bound by theory, think that the existence of silicate anion has further improved the catalytic performance of catalyst complex.Described silicate anion for example can provide Siliciumatom to repair the defective in the molecular sieve.Therefore, this can cause the extra stabilization of catalyzer under harsh hydrothermal condition.
As a result, described metal silicate plays the effect of catalytic promoter.
Described metal silicate can comprise a kind of alkaline-earth metal that surpasses that is selected from Ca, Mg, Sr and Ba.
Described metal silicate also can comprise other metal that is selected from following one or more: Ga, Al, Ce, In, Cs, Sc, Sn, Li, Zn, Co, Mo, Mn, Ni, Fe, Cu, Cr, Ti and V.Preferably, described other metal is selected from following one or more: Al, Mg, Ce, Co and Zn or its mixture.These two-, three-or many metal silicates can be synthetic according to any method as known in the art.This can be for example by the ion-exchange in solution or in solid-state (Labhsetwar etc., Reactivity of Solids, Vol.7, Issue 3,1989,225-233).
Described silicate anion can be present in the solid metal silicate in any form.Example comprises SiO
3 2-, SiO
4 4-, Si
2O
7 6-, Si
3O
10 8-Deng.
Preferred catalytic promoter can be the Calucium Silicate powder with pore structure of opening very much and can reaching.Even preferred catalytic promoter comprises having chemical constitution Ca
6Si
6O
17(OH)
2The synthetic crystallization calcium silicate hydrate, it (has molecular formula 6CaO.6SiO corresponding to known mineral xonotlite
2.H
2O).
Usually, synthetic hydrated silicon acid calcium is hydro-thermal ground synthetic under autogenous pressure.Particularly preferred synthetic hydrated silicon acid calcium can be purchased with trade(brand)name Promaxon from the Promat company of German Ratingen.
For the thermostability that proves xonotlite and therefore xonotlite as the suitability of the catalytic promoter among MTO and the OC, the commercial xonotlite that will sell with trade(brand)name Promaxon D in ambient air in calcining 24 hours under about 50% relative humidity under 650 ℃.Initial xonotlite has crystallization phases Ca
6Si
6O
17(OH)
2, the BET surface-area is 51m
2/ g and (less than 100nm's) pore volume are 0.35ml/g.After 650 ℃ were calcined down, this carrier kept its crystallinity corresponding with xonotlite.Therefore, after the calcinings in 24 hours under 650 ℃, crystallization phases still comprises xonotlite (Ca
6Si
6O
17(OH)
2), the BET surface-area is 47.4m
2/ g and (less than 100nm's) pore volume are 0.30ml/g.
Other example that comprises the metal silicate of alkaline-earth metal comprises CaAl
2Si
2O
8, Ca
2Al
2SiO
7, CaMg (Si
2O
6)
x, with and composition thereof.
With before described molecular sieve mixes, described metal metasilicate salt compound can (phosphorus be floating, phosphatation) and modification by calcining, decatize, ion-exchange, dipping or phosphatization.Described metal silicate can be independent compound or can be the part of blended compound.
Can with the cofabrication step of the blend of described molecular sieve or each material in-situ blending in reaction medium that before XTO or OC method, will prepare separately described metal silicate be contacted with described molecular sieve by described metal silicate.Described contact can realize by described molecular sieve and the described mechanical blending that comprises the metal silicate of alkaline-earth metal.This can be undertaken by any known blend method.Blend sustainable from 1 minute to be up to 24 hours, preferred 1 minute～10 hours time.If original position is not carried out in XTO or OC reactor, then can in the batch-type mixing tank or with continuation method, for example in forcing machine such as single screw rod or twin screw extruder, under vacuum or high pressure, carry out under 20～300 ℃ the temperature.Described contact can be carried out in water or non-aqueous media.Before described preparation steps, can be added with other compound that helps described preparation, as the thickening material or the polyelectrolyte of the cohesion that improves precursor (cohesion), dispersion and flowing property.Under oil droplet or spray-dired situation, make suitable liquid (high water content).In another embodiment, described contact is carried out in the presence of P contained compound.In embodiment, described contact is lower than 5 at pH, carry out in more preferably less than 3 water medium.
Before forming the preparation steps of described mixture, afterwards or simultaneously, other component can be randomly and described molecular sieve blend.In embodiment, can be with described molecular sieve and other combination of materials that extra hardness or catalytic activity is provided to the catalyst product of finishing.Can be the body material and/or the various binder material of various inertia or catalytic activity with the material of described molecular sieve blend.Such material comprises for example aluminum oxide of clay, silicon-dioxide and/or metal oxide.The latter is for naturally occurring or be to comprise the gelatinous precipitate of mixture of silicon-dioxide and metal oxide or the form of gel.In embodiment, some binder materials also can play thinner and make the speed that transforms to product in order to the control raw material and therefore improve selectivity.According to an embodiment, described binding agent also improves the wearing and tearing of described catalyzer under the industrial operation condition.
The naturally occurring clay that can be used as binding agent is for for example from the clay of kaolin families or polynite class.The virgin state that such clay can be exploited is used or they can carry out for example calcining of various processing, acid treatment or chemical modification before use.
Except above-mentioned, can be included in other material in the catalyst complex of the present invention comprise various forms of metals, phosphoric acid salt (metal phosphate for example, wherein said metal are selected from following one or more: Ca, Ga, Al, Ca, Ce, In, Cs, Sr, Mg, Ba, Sc, Sn, Li, Zn, Co, Mo, Mn, Ni, Fe, Cu, Cr, Ti and V), aluminum oxide or alumina sol, titanium dioxide, zirconium white, quartz, silicon-dioxide or silicon dioxide gel, with and composition thereof.Possible phosphatic example comprises amorphous calcium phosphate, mono-calcium phosphate, Lin Suanergai, Lin Suanergai dehydrate, α-or bata-tricalcium phosphate, octocalcium phosphate, hydroxyapatite etc.
The example of the adhesive oxides composition of possible binary comprises silica-alumina, silicon-dioxide magnesium oxide, silicon-dioxide-zirconium white, silica-thorium oxide, silica-beryllia, silica-titania, calcium-aluminum oxide.The example of ternary adhesive composition comprises for example calcium-silica-alumina or silica-alumina-zirconium white.
These components are being effective aspect the intensity that improves catalyst density and the raising catalyzer of preparing.The catalyzer that can use in fluidized-bed reactor has spheric shape basically, and it typically forms by spraying drying.Usually, the size of granules of catalyst can be about 20～500 μ m, more preferably 30～100um.In the described catalyst complex crystalline size of contained molecular sieve preferably less than about 10 μ m, be more preferably less than about 5 μ m and most preferably less than about 2 μ m.The amount of contained molecular sieve is 10～90 weight % of total catalyst mixture, preferred 20～70 weight % in the final catalyst mixture.
According to another embodiment, unmodified molecular sieve is at first prepared with binding agent and body material, uses phosphorus and alkaline earth metal silicate modification then.
According to further embodiment, during preparation steps, make randomly dealuminzation of molecular sieve, use the phosphorus modification then.The introducing of alkaline earth metal silicate can be carried out during preparation steps or the solid of being prepared be carried out.
According to preferred implementation, molecular sieve is dealuminzation and use the phosphorus modification at first randomly, then preparation.The introducing of described metal and phosphorus modification procedure are carried out simultaneously and/or the catalyzer of having prepared are carried out.
After preparation, described catalyst complex can further be handled, and comprises further decatize, leaching, washing, drying, calcining, dipping and ion-exchange step.If in the described before molecular sieve phosphorus modification of preparation steps (that is, metal silicate being incorporated into the step of molecular sieve) of blend, it can carry out after such step.
According to the special characteristic of this second embodiment, described molecular sieve is phosphorus modification (P-modification) zeolite.Above described phosphorus modification (P-modification) zeolite is described.
About the 3rd embodiment of the present invention, described molecular sieve is described in described second embodiment.In P-modification and/or alkaline-earth metal or rare-earth metal modified (M-modification) before, described molecular sieve can further be handled, and comprises decatize, leaching (for example, acidleach is got), washing, drying, calcining, dipping and ion-exchange step.In addition or alternatively, these steps also can be carried out during the P-modification or afterwards.Ion-exchange step refers in this article according to techniques well known in the art and substitutes the cationic at least a portion that comprises at first in the crystalline structure with various other positively charged ions.Place of cation can be hydrogen, ammonium or other metallic cation, comprises so cationic mixture.
For the present invention, if selected molecular sieve is not P-modification, then must before the M modification or during carry out with the modification of phosphorus molecular sieve.Preferably, described P-modification is undertaken by the leaching step of the acidic solution (preferably phosphoric acid solution) in any P of containing of the use source after the dealuminzation steaming step.Preferably, the P-modified molecular screen comprises the phosphorus of at least 0.3 weight % of described molecular sieve.
According to an embodiment of the invention, described molecular sieve can be according to the method that comprises the following steps that provide in the following order phosphorus modification:
-molecular sieve decatize 0.01～200 hour under 400～870 ℃ temperature;
-under the condition of from described molecular sieve, removing signal portion Al and the phosphorus of at least 0.3 weight % that introduces described molecular sieve effectively, leach with the aqueous acid solution that contains the P source;
Then, can carry out further modification according to the following steps that provide in the following order:
-with solid and liquid separation;
-optional washing step, or optional drying step, or optional drying step and washing step afterwards;
-calcining step.
Preferably, washing that separates, chooses wantonly and drying step and calcining are to carry out after the compound that will contain M is incorporated in the described molecular sieve.Metal M can be any alkaline-earth metal or rare earth metal.Preferably, described alkaline-earth metal is Ca.Yet, also can use Mg, Sr and Ba.Possible rare earth metal comprises La and Ce.
In the steam treatment step, temperature is preferably 420 ℃～870 ℃, more preferably 480～760 ℃.Pressure is preferably normal atmosphere and water partial pressure can be 13～100kPa.Steam atmosphere preferably contains 5～100 volume % steam and 0～95 volume % rare gas element, preferred nitrogen.Described steam treatment was preferably carried out 0.05～200 hour, more preferably carried out 0.05～50 hour.Those skilled in the art know usually, and the steam treatment of molecular sieve produces to be left described framework of molecular sieve and be present in the hole of described molecular sieve as aluminum oxide and the aluminium outside the hole.Dealuminzation and this term that this conversion is called molecular sieve will use in the text.
Handle the dissolving that causes aluminum oxide outside the skeleton through the molecular sieve of decatize with acidic solution.This conversion is called leaching and this term will use in the text.Advantageously under the reflux conditions of the boiling temperature that means solution, carry out with the leaching that the aqueous acid solution that contains the phosphorus source carries out.
The amount of described acidic solution advantageously is 2～10 a liters/kg molecular sieve.During the typical leaching is about 0.5～24 hour.Advantageously, the pH of the aqueous acid solution that contain P source of leaching in the step is 3, advantageously is 2 or lower.Advantageously, described aqueous acid solution is following solution: the mixture of the salt of the mixture of the acid of phosphorus, the acid of phosphorus and organic or inorganic acid, the acid of phosphorus and organic or inorganic acid (salt).The acid of phosphorus or corresponding salt can be phosphate radical ([PO
4]
3-, trivalent) and type, orthophosphite ([HPO
3]
2-, divalence) and type or Hypophosporous Acid, 50 root ([H
2PO
2]
1-, monovalence) and type.In described phosphate radical type, also can use gen-diphosphate or multi-phosphate ([P
nO
3n+1]
(n+2)-).Other organic acid can comprise organic acid for example citric acid, formic acid, oxalic acid, tartrate, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, toxilic acid, phthalic acid, m-phthalic acid, fumaric acid, complexon I, HEDTA, ethylenediamine tetraacetic acid (EDTA), trichoroacetic acid(TCA), trifluoroacetic acid or the salt (for example sodium salt) of such acid or the mixture of two or more such acid or salt.Other mineral acid can comprise mineral acid for example nitric acid, hydrochloric acid, methane sulfuric acid, sulfuric acid or the salt (for example sodium salt or ammonium salt) of such acid or the mixture of two or more such acid or salt.
The acid that has been found that phosphorus outside the complexing skeleton aluminum oxide and therefore it is removed from described molecular sieve solid material aspect in be very effective.The more substantial phosphorus of expecting during unexpectedly, than the acid solution that can be filled with employed phosphorus by the hole of the typical pore volume of molecular sieve and putative molecule sieve is stayed in the solid molecular sieves material.Two kinds of factors (being the reservation of dealuminzation and P) make the lattice aluminium in the zeolite lattice stable, thereby avoid further dealuminzation.This causes the adjustment of higher hydrothermal stability, molecular sieve character and the adjusting of acid matter, thereby improves the selectivity of molecular sieve.The dealuminzation degree can be regulated by decatize and leaching condition.
Advantageously, the final P content of molecular sieve is at least 0.3 weight % and be preferably 0.3～7 weight %.Advantageously, from described molecular sieve, extract and remove at least 10% Al by leaching.By the P concentration of leaching in the solution, the separation condition during solid and the liquid separation and/or during the washing procedure of choosing wantonly that also can flood and/or adsorb regulate residual P content.Can between separation and/or washing step, design drying step.
Then, described molecular sieve is separated with washing soln or be dried and do not separate with washing soln.Described separation is advantageously undertaken by filtration.Calcine described molecular sieve then, for example calcined 2～10 hours down at 400 ℃.
The M-modification of described molecular sieve is carried out the molecular sieve of P-modification or during the P-modifying process/is carried out afterwards.The P-modification can be carried out as mentioned above, and wherein said sieve is by the decatize dealuminzation, then with the acidic solution leaching that contains P.In the case, advantageously, the processing of described molecular sieve being carried out with the solution that contains M after leaching or washing step (that is, adding phosphorus compound and carried out the P-modification after) and before separating step, carry out.Yet M also can design to the introducing of described molecular sieve:
-during the leaching step,
-before the washing step but the leaching and drying after
-to contacted with P through the incinerating molecular sieve
-to not leaching as yet to introduce the molecular sieve that P has still contacted with P during washing step
Can be to the introducing of the M of described molecular sieve by being undertaken by the dipping or the absorption of the aqueous solution of the compound that contains M.
The introducing of the compound of the described M of containing can be carried out to the temperature that is up to the solution boiling point in envrionment temperature.
The compound concentrations that contains M described in the solution for 0.05M at least, be preferably 0.05～1.0M.The amount of alkaline-earth metal in the described M-P-molecular sieve or rare earth metal (M) can be at least 0.05 weight %, preferred 0.05～7 weight %, 0.1～4 weight % most preferably.
Before the preparation of described catalyst complex, described molecular sieve can further be handled, and comprises decatize, leaching (for example, acidleach is got), washing, drying, calcining, dipping and ion-exchange step.In addition or alternatively, these steps also can be carried out after the preparation of described catalyst complex.
Described alkaline-earth metal or rare earth metal M preferably are selected from following one or more: Mg, Ca, Sr, Ba, La, Ce.More preferably, M is an alkaline-earth metal.Most preferably, M is Ca.Particularly, under the P-modification situation by decatize and leaching, M can be rare earth metal for example La and Ce.
The compound of the described M of containing is preferably following form: organic compound, salt, oxyhydroxide or oxide compound.When described compound was contacted with described molecular sieve, described compound was preferably the solubilisate form.Perhaps, can after making described molecular sieve and the compound of the described M of containing contacts, form the solution of the compound of the described M of containing.
The possible compound that contains M comprise the metal M compound for example metal M vitriol, formate, nitrate, acetate, halogenide, oxyhalogenide, borate, carbonate, oxyhydroxide, oxide compound with and composition thereof.These can be for example calcium sulfate, calcium formiate, nitrocalcite, lime acetate, calcium halide, zirconyl oxyhalides calcium, lime borate, lime carbonate, calcium hydroxide, calcium oxide or its mixture.
The compound of the described M of containing also can contain other metal that is selected from following one or more: Mg, Sr, Ba, Ga, Al, Ce, In, Cs, Sc, Sn, Li, Zn, Co, Mo, Mn, Ni, Fe, Cu, Cr, Ti and V.The compound of the described M of containing also can comprise phosphorus in addition.
Can make those compound dissolutions that contain M of poorly water-soluble to form the solution of good solutionization by heating and/or by the pH that changes solution via the corresponding ammonium salt that adds phosphoric acid, acetate or nitric acid or described acid.The described compound concentrations that contains M is 0.05M at least.
Described alkaline-earth metal and rare earth metal M particularly Ca have the big hydration radius of a ball under hydration status.Therefore, be not wishing to be bound by theory, think and take place very lentamente with the ion exchange reaction that is positioned at the acid sites on the microvoid structure inside of molecular sieve.As a result, selected metal M only makes the acid sites on the outside surface that is positioned at described molecular sieve expose, and therefore improves described selectivity of catalyst.
Under the situation of P-modified molecular screen, the M-modification causes forming on the outer surface blended M-Al-phosphoric acid salt.Consider that phosphorus and alkaline earth or rare earth metal M binding ratio and Al are strong, this modification causes the stabilization of the phosphorus on the least stabile molecular sieve outer surface of phosphorus therein.Yet necessary is that all M atoms that are positioned on the described outside surface are saturated by phosphorus.This can be in the presence of excessive phosphorus and is guaranteed by the existence at the M that for example is used to wash off the solution form that inlet that excessive phosphorus prevents micropore stops up.
In case obtained the M-P-modified molecular screen, then can carry out the preparation of catalyst complex, promptly other component can be randomly and described molecular sieve blend.Yet (, described M-P-modified molecular screen also can be used as catalyzer like this.)
According to an embodiment, the molecular sieve of M-P-modification of preparation is mixed with catalyst complex altogether with the molecular sieve of M-P-as described herein that comprises at least 10 weight % and with respect to the M of at least 0.05 weight % of the weight of described molecular sieve and the phosphorus of at least 0.3 weight %.
In embodiment, can be with described molecular sieve and other combination of materials that extra hardness or catalytic activity is provided to the catalyst product of finishing.Can be the body material and/or the various binder material of various inertia or catalytic activity with the material of described molecular sieve blend.Such material comprises for example aluminum oxide of clay, silicon-dioxide and/or metal oxide.
According to another embodiment, unmodified molecular sieve is at first prepared with binding agent and body material, uses phosphorus and metal-modified then.
According to embodiment, during preparation steps, make randomly dealuminzation of molecular sieve, use the phosphorus modification then.The introducing of described metal can be carried out during preparation steps or the solid of preparing is carried out.
According to preferred implementation, molecular sieve is dealuminzation and use the phosphorus modification at first randomly, then preparation.The introducing of described metal with carry out simultaneously with the phosphorus modification procedure and/or the catalyzer of preparing carried out.
Described catalyst complex also can randomly comprise binding agent and/or body material and/or metal phosphate.Preferably, the amount of contained molecular sieve can be 10～90 weight % of total catalyst mixture, more preferably 20～70 weight % in the final catalyst complex.M concentration height in the catalyzer of being prepared in the comparable independent molecular sieve of the concentration of M is because described binding agent or body material also can contain some M compounds.
The naturally occurring clay that can be used as binding agent is for for example from the clay of kaolin families or polynite class.The virgin state that such clay can be exploited is used or they can carry out various processing, for example calcining, acid treatment or chemical modification before use.
Except above-mentioned, can be included in other material in the catalyst complex of the present invention comprise various forms of metals, phosphoric acid salt (metal phosphate for example, wherein said metal are selected from following one or more: Ca, Ga, Al, Ca, Ce, In, Cs, Sr, Mg, Ba, Sc, Sn, Li, Zn, Co, Mo, Mn, Ni, Fe, Cu, Cr, Ti and V), aluminum oxide or alumina sol, titanium dioxide, zirconium white, quartz, silicon-dioxide or silicon dioxide gel, with and composition thereof.Possible phosphatic example comprises for example mono-calcium phosphate, Lin Suanergai, Lin Suanergai dehydrate, α-or bata-tricalcium phosphate, octocalcium phosphate, hydroxyapatite etc. of amorphous metal phosphoric acid salt and metal phosphate such as calcium phosphate.
The example of possible binary adhesive composition comprises silica-alumina, silicon-dioxide magnesium oxide, silicon-dioxide-zirconium white, silica-thorium oxide, silica-beryllia, silica-titania, calcium-aluminum oxide and Calucium Silicate powder.The example of ternary adhesive composition comprises for example calcium-silica-alumina or silica-alumina-zirconium white.
About the XTO reaction zone, in the method, the raw material of organic compound that contains oxygen, halide or sulfur-bearing particularly contacts above-mentioned catalyzer under the condition of ethene and propylene producing light olefin effectively in the reaction zone of reactor.Typically, the described organic raw material that contains oxygen, halide or sulfur-bearing is contacted during for gas phase with described catalyzer when the described organic compound that contains oxygen, halide or sulfur-bearing.Perhaps, described method can be carried out in liquid phase or blended gas phase and liquid phase.In the method, transform the organic compound that contains oxygen, halide or sulfur-bearing, can in wide temperature range, produce alkene usually.Effectively operating temperature range can be about 200 ℃～700 ℃.At the lower end of described temperature range, it is slow significantly that the formation of required olefin product can become.At the upper end of described temperature range, described method can not form best product amount.At least 300 ℃ and to be up to 600 ℃ service temperature be preferred.
Pressure also can change in wide region.Preferred pressure is about 5kPa～about 5MPa, and most preferred scope is about 50kPa～about 0.5MPa.Aforementioned pressure refers to the described dividing potential drop that contains oxygen, halide, organic compounds containing sulfur and/or its mixture.
Described method can be carried out in any system that uses various fluidized-bed reactors.Expectation is this reaction method of operation under high space velocity especially.Described method can be carried out in many reaction zones of single reaction district or serial or parallel connection layout.After certain runtime, described catalyzer needs regeneration.This regeneration is carried out in the breeding blanket.Commercial-scale reactor assembly can be at 0.1h
-1～1000
-1Down operation of weight hourly space velocity (WHSV).
In the raw material of described XTO reaction zone, can there be one or more inert diluents, for example with the amount of 1-95 mole %, based on all raw materials that are fed to described reaction zone and the total mole number of thinner composition.Typical thinner comprises, but is not necessarily limited to, helium, argon gas, nitrogen, carbon monoxide, carbonic acid gas, hydrogen, water, paraffin, alkane (particularly methane, ethane and propane), aromatic substance, with and composition thereof.Preferable absorbent is water and nitrogen.Water can liquid or the injection of steam form.
The use of thinner can provide two advantages.First advantage is that it reduces the dividing potential drop of X and therefore improves selectivity to light olefin (mainly being propylene).The result can use lower temperature of reaction.Usually, the dividing potential drop of X is low more, and the light olefin selectivity is high more.Depend on dividing potential drop, temperature of reaction and catalyst property, have the optimum value of light olefin productive rate.
Second advantage using thinner is the low-temperature receiver that its X that can be used as heat release transforms.Therefore, higher more than molecular heat capacity, the absorbable heat of thinner is many more.This second advantage can be not too important under the situation of fluidized-bed reactor, because the known flow fluidized bed reactor is near the excellent reactor that moves under the uniform temperature in whole catalyst bed.Preferably, described thinner can easily separate with described light olefin product, preferentially by simply being separated.Therefore, preferable absorbent is a water.Thinner can combined feed (X+ thinner) 1～95 mole of %, preferred 10～75 moles of % add.
According to embodiment, there is not water (or steam) to inject basically as the thinner of the raw material that is delivered to described XTO reactor.Yet, this means that described raw material can contain the suitable steam that flows and clean of catalyzer that has been contained in the water in the fresh organic raw material that contains oxygen, halide or sulfur-bearing or has been used for making the fluidized-bed reactor of XTO reactor.
Described oxygen-containing compound material is to contain the molecule that has at least one Sauerstoffatom and can be converted into olefin product in the presence of above catalyzer or any raw material of any chemical.Described oxygen-containing compound material comprises at least a organic compound that contains at least one Sauerstoffatom, for example fatty alcohol, ether, carbonyl compound (aldehyde, ketone, carboxylic acid, carbonic ether, ester etc.).Representational oxygenatedchemicals comprises, but is not necessarily limited to rudimentary straight chain and branched aliphatic alcohol and their undersaturated counterpart.The example of suitable oxygenatedchemicals includes, but are not limited to: methyl alcohol; Ethanol; N-propyl alcohol; Virahol; C
4-C
20Alcohol; Methyl ethyl ether; Dimethyl ether; Anaesthetie Ether; Di Iso Propyl Ether; Formaldehyde; Methylcarbonate; Dimethyl ketone; Acetate; With and composition thereof.Representational oxygenatedchemicals comprises rudimentary straight or branched fatty alcohol, their unsaturated counterpart.Similar with these oxygenatedchemicalss, can use sulfur-bearing or halid compound.The example of suitable combination thing comprises methyl mercaptan; Dimethyl thioether; Ethanethio; The diethyl thioether; Monochlorethane; Monochloro methane; Methylene dichloride; Have the positive alkyl halide of the positive alkyl that comprises about 1～about 10 carbon atoms, positive alkyl sulfide; With and composition thereof.Preferred oxygenatedchemicals is methyl alcohol, dimethyl ether or its mixture.
In the XTO effluent, in having the alkene of 4 or more a plurality of carbon atoms, there is the butylene that surpasses 50 weight %.
About the effluent of described XTO method, " light olefin " refers to that ethene and propylene and " heavy hydrocarbon fractions " are defined as the cut that contains the high hydrocarbon of molecular weight ratio propane in this article, and it means to have 4 or more a plurality of carbon atom and note is made C
4 +Hydrocarbon.Described C
4 +The azeotropic that cut also can contain other contains the compound of X, as methyl alcohol and other oxygenatedchemicals.
The heavy hydrocarbon fractions that conversion produces in described XTO reactor in described OC reactor is to produce the ethene and the propylene of additional quantity.
About the OC reaction zone, various reaction paths can occur on the described catalyzer.Have about 400～600 ℃, preferred 520～600 ℃, also more preferably 540～580 ℃ temperature in and 0.1～2 crust, most preferably from about under the processing condition of atmospheric olefin partial pressures.The olefin catalytic cracking can be regarded as and comprises via bond rupture and produce the more process of short molecule.
In the catalytic cracking process of described OC reactor, select processing condition with provide required to the highly selective of propylene or ethene, in time stable conversion of olefines and effluent in stable olefin product distribute.Help low pressure, high temperature in and short duration of contact such purpose, described processing parameter all is to be mutually related and total cumulative effect is provided.
Select processing condition to be unfavorable for causing forming the hydrogen transfer reactions of paraffinic hydrocarbons, aromatic hydrocarbons and coke precursors.Therefore, described process conditions adopts high space velocity, low pressure and high temperature of reaction.LHSV is 0.5～30h
-1, preferred 1～30h
-1Olefin partial pressures is 0.1～2 crust, preferred 0.5～1.5 crust (referring to absolute pressure in this article).Particularly preferred olefin partial pressures is normal atmosphere (i.e. 1 crust).Described heavy hydrocarbon fractions raw material preferably is being enough to described raw material conveying by charging under the main entrance pressure of reactor.Described raw material can not dilute or charging under the situation that rare gas element for example dilutes in nitrogen or the steam.Preferably, the total absolute pressure in this second reactor is 0.5～10 crust.Use low olefin partial pressures for example normal atmosphere be tending towards reducing the incidence of hydrogen transfer reactions in the cracking process, this reduces the possibility that the coke that is tending towards reducing catalyst stability forms again.The cracking of alkene preferably 400～650 ℃, more preferably 450～600 ℃, also more preferably carry out under 540～590 ℃ the feed(raw material)inlet temperature.
The conversion of heavy olefins is highly heat absorption, and therefore compares the temperature that reduces reaction product and catalyzer with material temperature.On the other hand, the conversion of compounds that contains X be the height heat release and therefore compare the temperature that increases reaction product and catalyzer with material temperature.Therefore, preferably, the part of raw materials of the described X of containing is delivered to described OC reaction zone with described heavy olefins.Preferred embodiment be to compare with material temperature, the temperature of reaction product and catalyzer descends near 0.Preferably, compare with the material temperature in the ingress of reactor, the reaction product of reactor exit and the temperature of catalyzer descend with 10～95% reducing that desired temperature when the compound that contains X not being added in the described heavy olefins raw material descends.Preferably, the combination raw materials of going to described OC reactor contains the organic raw material that contains oxygen, halide or sulfur-bearing that is less than about 30 weight %.
Described OC reactor zone also is a fluidized-bed.The example of fluidized-bed reactor is for being used for the FCC type fluidized-bed reactor of fluid catalystic cracking in refinery.Described heavy hydrocarbon fractions cracking process absorbs heat, and therefore, described reaction zone should be suitable for if necessary supplying heat to keep suitable reaction temperature.
The part of described catalyzer takes out and is delivered to the breeding blanket continuously or off and on from described conversion reactor (XTO).After regeneration, will be delivered to described OC reaction zone continuously or off and on through at least a portion of regenerated catalyzer.By injecting oxygenous logistics on the described catalyzer so that the sedimentary coke burning on the described catalyzer is regenerated under the sufficiently high temperature.
Described OC reactor effluent comprises methane, light olefin and has the hydrocarbon of 4 or more a plurality of carbon atoms.Advantageously, described OC reactor effluent is delivered to fractionator and reclaims described light olefin.Advantageously, in the recirculation of the ingress of described OC reactor, it randomly mixes with the heavy hydrocarbon that reclaims from the effluent of described XTO reactor with at least a portion of described hydrocarbon with 4 or more a plurality of carbon atoms.Advantageously, before the described hydrocarbon with 4 or more a plurality of carbon atoms of the ingress of described OC reactor recirculation, described hydrocarbon with 4 or more a plurality of carbon atoms is delivered to the after-fractionating device to remove heavy component.In a preferred embodiment, the light olefin that the light olefin that will reclaim from the effluent of described XTO reactor and the fractionator after described OC reactor reclaim shared (common, common) handle in the recovery zone.
In another embodiment, described OC reactor effluent and described XTO reactor effluent are mixed and deliver to fractionator, perhaps deliver to same fractionator, and reclaim light olefin.At least a portion of hydrocarbon that will have 4 or more a plurality of carbon atoms is in the recirculation of the ingress of described OC reactor.Advantageously, before the recirculation of the ingress of described OC reactor, carry the after-fractionating device to remove heavy component described hydrocarbon at described hydrocarbon with 4 or more a plurality of carbon atoms with 4 or more a plurality of carbon atoms.The light olefin that is reclaimed is handled in recovery zone, and described recovery zone is also referred to as shared recovery zone in above paragraph.
If described OC reactor feedstocks contains diene, then recommend to make described raw material carry out selective hydrogenation process to remove described diene.
Advantageously, the paraffinicity in the described raw material of the ingress of described OC reactor is at least 20 weight %, preferably at least 30%, more preferably 40% on the carbon back plinth.Advantageously, the paraffinicity in the described raw material of the ingress of described OC reactor is no more than 80 weight %.
About reactor, for example XTO and OC reactor are used for some chemical reactors, and fixed-bed reactor can have big shortcoming.When fast and height heat release or heat absorption, focus or cold spot will emerge and make the reactor performance deterioration in this packed bed when reaction.Also sintering, obstruction and fluid distribution inequality can take place much easierly, particularly when sedimentation of coke is quite fast in packed bed.When reacting height heat release especially or heat absorption, to compare with fixed bed, fluidized-bed can provide significant advantage.In case the solid fluidisation in the described bed, the solid in the then described bed will show almost as liquid.Bubble size in the described fluidized-bed, shape, formation, lift velocity and coalescent (coalescence) have with liquid in those quantity similarity of bubble.
Therefore, the behavior of the liquid-like of fluidized-bed allows that solid handles as fluid, and successive charging and take out the possibility that therefore becomes.(strictness rigorous) mixes and causes uniform temperature, even also be so for the reaction of height heat release or heat absorption, and therefore provides reactor control more stably for violent in the fluidized-bed.Described violent mixing also improves solid and contacts with fluid, and its enhance heat transfer and mass transfer.
The modification of many different fluidized-beds is arranged in practice, and it is included in available technical manual (for example, Handbook of fluidization and fluid-particle system, Taylor﹠amp; Francis GroupLLC, 2003) in.The fluidisation phenomenon of gas-solid system depends on the type of the powder that is adopted very much.There are some classification, all based on the original work of Geldart.The many catalyzer that use in the fluidised bed system are category-A particle (Group Aparticles), it is characterized in that after minimum fluidisation expanding mutually with close before the beginning bubbling.Bubble appears under minimum bubbling velocity.
Streaming mode can be divided into the two kinds of wide in range types-formula (steadily) of loosing and poly-formula (bubbling).In particulate fluidization, solid particulate is evenly dispersed in the fluidizing medium and the bubble that do not have to recognize easily usually relatively.Therefore, particulate fluidization is also referred to as even fluidisation sometimes.In non-homogeneous or aggregative fluidization, do not contain solid space (bubble) and form usually and in bubbling fluidized bed or in slugging bed, observe.For gas-solid system, have several differentiable streaming modes: fixed bed, particulate fluidization, bubbling fluidization, turbulent fluidisation and turbulence fluidisation, in them each, standard is available.When being higher than transfer rate, operating speed makes the particulate of carrying secretly recirculate to keep that when bed necessary, other streaming mode is possible.
Formula mode: U looses
Mf≤ U＜U
Mb
For category-A powder (Group A powders), fixed bed is at minimum fluidization velocity (U
Mf) more than expand equably (particulate fluidization) and as long as this speed keeps below minimum bubbling velocity (U
Mb), then do not observe bubble.
Bubbling mode: U
Mb≤ U＜U
Ms
When gas velocity being increased to minimum bubbling velocity (U
Mb) bubble appears when above.Bubble forms above sparger, coalescent and growth.The bubbling mode is characterised in that bubble coexists mutually with close/emulsification mutually.Most of fluidizing agent exists with bubble form, and the result to pass the gas velocity of close phase very low.
Turbulent mode: U
Ms≤ U＜U
c
Adopt the bed ratio of big height to diameter, the chien shih bubble gathered into bigger bubble when described bed provided enough.When air bubble growth when being about the size of a cross section, described bed enters turbulent mode, the periodicity with air pocket is by the big fluctuation of the rule of falling with bed pressure.Speed U
cReach its maximum diameter and the pressure surge amplitude bed operational condition when the highest corresponding to aeroembolism (slug) wherein.
Transition to the turbulence mode: U
c≤ U＜U
k
When continuous raising gas velocity to this speed U
cWhen above, air pocket begins to be broken into less bubble, has less pressure surge.This speed note is made U
k, and characterize from the transition of bubbling mode to the turbulence mode.
Turbulence mode: U
k≤ U＜U
Tr
Until transfer rate (U
Tr), described bed all is in the turbulence mode.Still there are bubble or space, although they in suspension are not too differentiable in densification.In this mode, the interaction between air void and the close/emulsification mutually is violent and effective gas-solid contact is provided.
Quick streaming mode: U＞U
Tr
Be higher than described transfer rate (U
Tr), particle begins to be carried secretly and under the situation of particulate replacement of not carrying secretly and taking out of or recirculation, operate continuously no longer may.Fast fluidized bed typically is characterised in that at the emulsion zone of the close sparger at place, bottom and the freeboard of fluidized bed at the top and coexists.Particle speed increases and therefore bed density reduction along with rising in bed.
Pneumatic transport: U＞＞U
Tr
All particles that are fed to fluidized-bed bottom transfer out with the dilute phase with the concentration that changes along bed height.Typical example is the riser tube fluidized-bed that uses during FCC uses.Riser tube is to have high height to make catalyzer as fluid phase with minimum back-mixing pass described riser tube than the vertical pipeline of (＞10) and ideal riser tube near the plug-flow condition to diameter.Usually, the minimum back-mixing of fluid phase is necessary for making the selectivity maximization in the chemical conversion.
In transportation flow fluidized bed reactor (quick fluidizing or pneumatic transport), core circulation can appear, and wherein the core that high speed is rare is surrounded by the closeer slowly ring of motion.Under low circulation mass flux, the solid in the ring flows downward at the wall place.Under high circulation mass flux, the solid in the ring upwards flows along wall.This uneven flow phenomenon will cause the catalyst performance of inefficient gas-solid contact and non-optimum, and significant gas and solid back-mixing will occur, particularly when existence flows downward in the wall zone.For quick fluidisation, can use internals (internals) so that axially and radial gas-solid flow structure redistribution, promptly improve gas-solid flow structure spatially homogeneity and so promote radial gas-exchange of solids.The transportation flow fluidized bed reactor need return granules of catalyst recirculation the bottom of this reactor.This provides the possibility of controlling the density of catalyst in the fluidized-bed by recirculation catalyzer more or less.
In the bottom of fluidized-bed, the cross section that feed fluid is crossed over reactor vessel distributes equably.At the end of reaction zone, by inflector (deflector), abscission zone and cyclonic separator with the reactive vapors and the catalyst separating of carrying secretly.Catalyzer is collected, from remaining hydrocarbon stripping, and can carry go back to the bottom of described fluidised bed zones via vertical tube and valve.
For the XTO reaction of heat release, the preferred leap (radial and axial ground) catalyst bed has uniform temperature to avoid the suitable control of focus and catalyzed reaction.This can realize by quick recirculation and the final back-mixing at the reactor vessel inner catalyst.The mode of control average reaction temperature is by introducing that temperature is lower than the raw material of described average bed temperature and/or by taking away heat by means of heat exchange from described catalyst bed.This heat exchange can realize that heat-eliminating medium flows through this internal heat exchange tubes and takes away heat from reactor vessel by internal heat exchange tubes; Perhaps this heat exchange can realize by the external heat exchange, and this external heat exchange is flowed around heat exchanger tube by the catalyzer that makes the heat of collecting from the top of reactor and will be got back to the described reactor vessel through the refrigerative catalyst recycle.
For the OC reaction of heat absorption, the uniform temperature of always preferably not crossing over catalyst bed is because when catalyzed conversion speed is low owing to the uniform lesser temps of catalyst bed, need the remarkable overheated so that required reaction heat to be provided of raw material.More allow the catalyzer that operates under the higher medial temperature, and allow by the thermocatalyst carried secretly and introduce required reaction heat by using high catalyst circulation rate as the reactor vessel of plug-flow.This thermocatalyst can be from the RS Regenerator Section that coke is burnt and therefore catalyzer absorbs the combustion heat, perhaps from the XTO conversion zone of wherein said catalyzer absorption from the reaction heat of the XTO reaction of heat release.During the OC thermo-negative reaction, described catalyzer release of heat and colder catalyst transport can be gone back to described MTO district wherein absorbs heat once more by the MTO reaction.
About catalyst regeneration, it is by remove the revivifier of the deposits of coke on the described catalyzer with oxygen combustion that the XTO/OC reactor assembly of combination also has main purpose.Revivifier is mainly turbulence or fast fluidized bed system.Typically, revivifier is included in the close catalyst bed of container bottom and rarer bed of close container top.Secondary combustion is when in CO and the dilute phase or the phenomenon in the residual oxygen in the dilute phase space of described container when reaction.The burning of CO discharges a large amount of heat, has catalyzer seldom simultaneously, and it is caused irreversible inactivation by overheated.There is two types revivifier, moves with the partial combustion mode operation or with full-burn mode.In the partial combustion pattern, provide the air that is less than stoichiometry to described revivifier.Most of carbon reaction becoming carbon monoxide and only a part of reaction become carbonic acid gas.Ideally, should consume whole oxygen and in flue gas, should not have oxygen.CO/CO in the flue gas
2Ratio typically be 0.5～2.0.In full-burn mode, provide excessive air to described revivifier.Ideally, should make all the carbon reactions in the coke become carbonic acid gas, and in flue gas, should not have carbon monoxide.On dry-basis, the residual oxygen content in the flue gas is 1.0～3.0%.The partial combustion revivifier has some advantages with respect to the perfect combustion revivifier, particularly when described catalyzer is responsive to high temperature and steam ambient: (i) because it need be less than the air of stoichiometry, therefore under the airflow of specified rate, can make more coke burning, (ii) discharge the less combustion heat and therefore moderate temperature control be possible, this keeps catalytic activity better in the presence of the steam that is produced by hydrogen burning.The latent defect of partial combustion revivifier is a residual coke higher on the regenerated catalyzer.Under perfect combustion regenerated situation, carbon residual on the catalyzer is low higher with the catalyst activity recovery.The latent defect of perfect combustion revivifier comprises because the higher heat release of perfect combustion reaction and more irreversible catalyst activity forfeiture therefore.Use two stage regeneration can reduce catalyst deactivation.In described two stage regeneration, the fs under moderate temperature, operate with mainly burn be present in the coke, have the more hydrogen and some carbon of high reaction rate.In subordinate phase, use excess air, make remaining carbon under higher temperature, burn into carbonic acid gas, and, therefore the catalyst deactivation under the high temperature is minimized owing in the subordinate phase revivifier, there is not water vapor.
Secondary combustion can occur in partial combustion pattern (regenerator bed of oxygen penetration densification) and full-burn mode (CO penetrates fine and close regenerator bed) among both, often because the skewness of catalyzer.Revivifier can be in the operation down of low temperature (＜650 ℃), medium temperature (＜700 ℃) and high temperature (～730 ℃).At low temperatures, perfect combustion is not feasible, but partial combustion can be stable.Under medium temperature, stable partial combustion is that possible and perfect combustion are possible, and condition is to add combustion improver.High temperature regeneration can partial combustion and both steady runnings of full-burn mode.Combustion improver or CO promotor help CO to be converted into CO fully at the close of revivifier in mutually
2With the temperature excursion that therefore prevents to cause owing to secondary combustion.These promotor can be improved the more homogeneous combustion of coke, particularly under the situation of uneven distribution between coke catalyzer and the air.Combustion improver is typically by constituting at the platinum on the alumina supporter (300-800wppm) and adding described combustion improver to reach the platinum of 0.5-1.5ppm in catalyst inventory.
Under the situation of XTO, need be for the XTO reaction in the additional heat of regeneration period generation, because the XTO reaction itself is strong heat release.On the other hand, extra heat can be used for the OC reaction zone, because the OC reaction is absorbed heat.If in revivifier, particularly under full-burn mode, produce, then can increase catalyst cooler to take away excessive heat more than the needed heat of reaction.Described catalyst cooler is the heat exchanger that produces steam when the catalyzer from revivifier is taken away heat.
Randomly, for the propylene of regulating whole process (XTO+OC) ratio, can make ethene in whole or in part in the recirculation of OC reactor and advantageously be converted into more propylene to ethene.This ethene can be from the segregation section of XTO reactor or from the segregation section of OC reactor or from the segregation section of the segregation section of XTO reactor and OC reactor or even from optional shared recovery zone.
Randomly,, can make ethene, therein ethylene and describedly contain oxygen, halide or the combination of sulfur-bearing organic raw material to form more propylene in whole or in part in the recirculation of XTO reactor for the propylene of regulating whole process (XTO+OC) ratio to ethene.This ethene can be from the segregation section of XTO reactor or from the segregation section of OC reactor or from the segregation section of the segregation section of XTO reactor and OC reactor or even from optional shared recovery zone.
These working method are allowed with identical equipment and catalyzer in response to the demand of propylene on the market to ethene.
The general flow chart of the catalyzer of Fig. 1 explanation between OC reaction zone, XTO reaction zone and breeding blanket.DME refers to dimethyl ether.For this figure for simplicity, the details of not shown each concrete equipment.
In XTO district (1), the compound that contains X that arrives via pipeline (2) is converted into hydrocarbon, and described hydrocarbon flows to depropanizing tower (20) via pipeline (15).Catalyzer from the inactivation in XTO district is gone to revivifier (4) via pipeline (3), wherein makes the catalyst regeneration of inactivation by burning.Get back to the XTO district through the regenerated catalyzer via pipeline (5).OC district (10) makes X, and (the heavy olefins cracking that arrives for methyl alcohol/DME) (82) with via pipeline (81) herein is for than light-weight alkene, describedly goes to depropanizing tower (70) than light-weight alkene via pipeline (16).Catalyzer in the OC district is delivered to revivifier (4) to regenerate by burning via pipeline (12).Get back to OC district (10) through the regenerated catalyzer via pipeline (11).Catalyzer also can be gone to XTO district (1) and go to OC district (10) from XTO district (1) via pipeline (14) on the contrary via pipeline (13) from OC district (10).Depropanizing tower (20) produces light ends and heavy ends, and described light ends is delivered to shared deethanizing column (30) via pipeline (21), and described heavy ends is delivered to OC district (10) via pipeline (22) and pipeline (81).Depropanizing tower (70) produces light ends and heavy ends, and described light ends is delivered to shared deethanizing column (30) via pipeline (71), and described heavy ends is delivered to rerunning tower (80) via pipeline (72).Rerunning tower (80) produces C4-C6 cut and C6+ cut, and described C4-C6 cut is recycled to OC district (10) via pipeline (81), and described C6+ cut is delivered to bank via pipeline (82).Deethanizing column (30) produces than light cut of propylene and the cut that mainly contains propylene and propane, the described cut lighter than propylene is delivered to demethanizing tower (40) via pipeline (31), and the described cut that mainly contains propylene and propane is delivered to C3 knockout tower (60) via pipeline (32).Propane product at the bottom of C3 knockout tower (60) generation cat head propylene product and the tower, described cat head propylene product is delivered to bank via pipeline (61), and the propane product is delivered to bank via pipeline (62) at the bottom of the described tower.The overhead product of demethanizing tower (40) (being mainly methane and hydrogen) is delivered to fuel gas system via pipeline (41).The bottom product of demethanizing tower (40) is delivered to C2 knockout tower (50) via pipeline (42).Ethane product at the bottom of C2 knockout tower (50) generation cat head ethylene product and the tower, described cat head ethylene product is delivered to bank via pipeline 51, and ethane product is delivered to bank via pipeline (52) at the bottom of the described tower.
Fig. 2 illustrates the more specifically embodiment of segregation section.The product in XTO district (1) flows to shared depropanizing tower (70) via the product of pipeline (15) and OC district (10) via pipeline (16).In this particular case, all heavy hydrocarbons that produce as the bottom product of depropanizing tower (70) are gone to rerunning tower (80) via pipeline (72).The remaining explanation with Fig. 1 is similar.
About catalyst recirculation, in embodiment, will be from all catalyst transport of revivifier to the OC reaction zone, further be delivered to then the XTO reaction zone and at last with all catalyst transport of XTO reaction zone to revivifier (breeding blanket) with to the OC reaction zone.
Fig. 3 illustrates that catalyzer flows to the OC reaction zone from the breeding blanket, flows to XTO reaction zone and the last embodiment that flows to the breeding blanket once more then.For simplicity, omit the details of vessel internals in the drawings.Document of this area and technician understand the requirement of vessel internals and utility appliance easily.X (is methyl alcohol/DME) be transported in the fluidized-bed XTO district (1) via pipeline (2) herein.In the top of XTO district (1), product separates in disengaging/cyclone separation (3) with catalyzer and product is delivered to segregation section via pipeline 4.Randomly, can extract the reaction heat that XTO produced between the reaction period by catalyst cooler (5).The XTO district receives catalyzer via pipeline (14) from OC district (10).(is that methyl alcohol/DME) and final ethene inject OC district (10) via pipeline (11) with C4+ hydrocarbon, X herein.Catalyzer, reactant and product are gone to disengaging/cyclone separation (12), wherein with product and catalyst separating.Product is delivered to segregation section via pipeline (13).Catalyzer takes out via pipeline (14) to XTO district (1) from disengaging/cyclone separation (12).The catalyzer that takes out inactivation from XTO district (1) via pipeline (6) to breeding blanket (20).Air injects via pipeline (21) and wherein makes deposits of coke incendiary breeding blanket (20).In disengaging/cyclone separation (22), combustion gases and catalyst separating and combustion gases are sent via pipeline (23).Randomly, because being the reaction of very heat release and the temperature of breeding blanket (20), the burning of deposits of coke needs careful control, catalyst cooler (24) can be installed, and thermocatalyst cycles through described catalyst cooler to be cooled, and it allows the temperature in the control breeding blanket (20).Be delivered to OC district (10) through the regenerated catalyzer via pipeline (25).
The more specifically embodiment of Fig. 4 explanatory view 3.Be present in the XTO district (1) and in disengaging/cyclone separation (3) with at least a portion of the isolating catalyzer of product via pipeline (7) be delivered to OC district (10) via the fresh of pipeline (25) through the regenerated catalyzer.Remaining is similar with Fig. 3.
Fig. 5 explanation is wherein for the embodiment of the shared disengaging/cyclone separation of XTO and OC district use product and catalyzer.Shared disengaging/cyclone separation (3) is positioned at the place, top in XTO district (1).The end in OC district (10) is connected to disengaging/cyclone separation (3), and wherein catalyzer separates with the product that produces in XTO district (1) and OC district (10) and is delivered to segregation section via pipeline 4.(20) are delivered to OC district (10) from the breeding blanket via pipeline (25) through the regenerated catalyzer.To separate with product with the catalyst mix of carrying secretly and shared disengaging/cyclone separation (3) from the catalyzer of OC district (10) and flow back into the XTO district via pipeline (5) (it also can randomly be made of catalyst cooler) from XTO district (1).The part of the catalyzer of this inactivation is delivered to breeding blanket (20) via pipeline (6).
The more specifically embodiment of Fig. 6 explanatory view 5, wherein disengaging/cyclone separation is at the top of OC district (10).(20) are delivered to OC district (10) from the breeding blanket via pipeline (25) through the regenerated catalyzer.At least a portion of catalyzer is delivered to XTO district (1) via pipeline 14 in the OC district (10).Catalyzer and product from XTO district (1) flow to shared disengaging/cyclone separation (12), wherein they with from the product and the catalyst mix of OC district (10).Isolating catalyzer is delivered to breeding blanket (20) via pipeline (15) in disengaging/cyclone separation (12).Be delivered to segregation section through product of mixing via pipeline 13.
The method of making olefin product by oxygen-containing compound material can comprise by the hydrocarbon polymer additional step of oil, coal, tar sand, shale, biomass, waste and Sweet natural gas manufacturing oxygen-containing compound material for example.The method of known manufacturing oxygen-containing compound material in this area.These methods comprise: be fermented into alcohol or ether; Make synthetic gas, then described synthetic gas is converted into alcohol or ether.Synthetic gas can pass through for example steam reformation, self-heating recapitalization and partial oxidation manufacturing of currently known methods under the situation of gas raw material, perhaps can make by reformation or the gasification of using oxygen and steam under the situation of solid (coal, organic waste) or liquid starting material.Methyl alcohol, dimethyl sulfide and methyl halide can be by making by means of the oxidation of dioxy, sulphur or halid methane in the organic compound that contains oxygen, halide or sulfur-bearing at this accordingly.
Those skilled in the art will also be understood that olefin product that the oxygenatedchemicals by use molecular sieve of the present invention makes to the reaction of conversion of olefines can be randomly and one or more comonomer polymerizations, to form polyolefine particularly polyethylene and polypropylene.The invention still further relates to described polyethylene and polypropylene.
[embodiment]
With zeolite ZSM-5 (Si/Al=13) sample that do not use template synthetic H form 550 ℃ of following decatizes 6 hours.Make through the solid of decatize and the H of 3.14M
3PO
4Solution under refluxad contacts 4 hours in (4.2ml/1g zeolite).Then, at room temperature make solid and liquid phase separation by filtering from solution.The material that is obtained is following dry 16 hours at 200 ℃.Make the sample of 10g drying contact 1 hour under the stirring at room temperature with 42ml water and 0.7g xonotlite (silicate of calcium).Then, in this solution, add low sodium silicon dioxide gel (2034DI Bindzil) of 30g and 2g kaolin.The gained mixture under agitation kept at room temperature 1 hour and dry again.The powder of drying was calcined 2 hours down at 700 ℃.Hereinafter this sample is called sample A.
Embodiment 2 (OC)
To carrying out catalyst test on 10ml (6.3g) granules of catalyst (35-45 order) of sample A in the tubular reactor that is loaded into internal diameter 11mm.Make contain acyclic basically alkene C4 (～60%) raw material in fixed-bed reactor in the presence of catalyzer at 575 ℃, LHSV=6.7h
-1, carry out catalytic cracking under the P=1.5 crust absolute pressure (bara).
The result of the average catalyst performance during initial 3 hours is in following table 1.Value in the table 1 is the weight % on the carbon back plinth.
Then, with catalyzer at N
2Flow (5Nl/h) cooling down, unload and pass through CHN methods analyst carbon content.Described catalyzer contains the carbon of 0.2 weight %.
The used catalyst sample that contains 0.2 weight % carbon that is unloaded is called sample B (pre-treatment in the OC reaction) hereinafter.
Table 1
Embodiment 3 (MTO reaction)
In fixed bed downflow system stainless steel reactor, to 2g catalyzer (35-45 order particle) with pure basically methanol feedstock, at 550 ℃ down with at the pressure and the WHSV=1.6h of 0.5 crust gauge pressure
-1Under carry out catalyst test.Before the catalysis operation, all catalyzer are at mobile N
2Heating is until temperature of reaction (5Nl/h).By the online product analysis that carries out of the gas chromatograph that is equipped with capillary column.At the catalytic performance of measuring catalyzer basically completely under the methanol conversion.
The regeneration of used catalyst under 550 ℃ at N
2Carry out in/the airflow (80/20) at least 10 hours during.Then, with described catalyzer N
2(5Nl/h) cleaned 1 hour.
In MTO reaction, estimate live catalyst A, the live catalyst A after 1 reaction/reprocessing cycle, catalyst B (preprocessed catalyst A in OC) and through pretreated in MTO reaction regenerated catalyst B afterwards.
Be given in the productivity of propylene on the carbon back plinth among Fig. 7.
The presentation of results P-ZSM-5 that provides among Fig. 7 in MTO reaction the good catalyst performance and in the OC reaction, at first use the catalyzer (sample B) of (pre-cokeization) to be used for the beneficial effect of MTO.In case the sample B after using in MTO is by coke burning holomorphosis and be used for MTO once more, then its performance become with the performance classes of live catalyst (sample A) seemingly, illustrate before live catalyst is used for MTO, at first to be used for the beneficial effect that OC reacts.
With zeolite ZSM-5 (Si/Al=13) sample that do not use template synthetic H form 550 ℃ of following decatizes 6 hours.600g is contained 34 weight %SiO through the sample of decatize and 37.5g xonotlite (silicate of calcium) and 330g
2Silicon dioxide gel (2034DI Bindzil) extrude together.Will be through the sample of moulding 400 ℃ of calcinings 6 hours down, and with the H of 1M
3PO
4Solution under refluxad contacts 4 hours in (4.2ml/1g zeolite).Then, will contain the solution cooling of described catalyzer, and at room temperature make solid and liquid phase separation by filtration.The material that is obtained was calcined 2 hours down 110 ℃ of following dryings 16 hours with at 700 ℃.
Hereinafter this sample is called sample C.
Embodiment 5-(OC test)
10ml in the tubular reactor that is loaded into internal diameter 11mm (6.2g) catalyzer C particle (35-45 order) is carried out catalyst test.Make the raw material that contains non-cyclic hydrocarbon C4 (63% alkene) basically at 575 ℃, WHSV=9.7h
-1, carry out catalytic cracking under the P=1.5 crust absolute pressure.
The result of the average catalyst performance between on-stream period in initial 5 hours is in table 2.Fig. 8 illustrates catalyzer C stabilizing active during 24 hours in the OC reaction.Described value is the weight % on alkene (CH2) basis in raw material.
Embodiment 6-contrast (using the OC test of blended material, 15%C4-C5 recirculation)
10ml in the tubular reactor that is loaded into internal diameter 11mm (6.2g) catalyzer C particle (35-45 order) is carried out catalyst test.Make contain 85 weight %MeOH and 10 weight % non-annularity C4 hydrocarbon (63% alkene) and 5 weight % basically the raw material of non-cyclic olefin C5 (59% alkene) in fixed-bed reactor at 550 ℃, WHSV=3.7h
-1, carry out catalytic cracking under the P=1.5 crust absolute pressure.
The result of the average catalyst performance between on-stream period in initial 5 hours is in table 2.Described value is the weight % on alkene (CH2) basis.
Embodiment 7-(MTO reaction)
Carry out the MTO test under the condition that catalyzer C is given in embodiment 3.
In table 2, provide the active result of average catalyst who is illustrated in 1-5 hour TOS on the dry basis of alkene (CH2) backbone.Described condition is called MTO hereinafter.Suppose that methyl alcohol contains the potential alkene (CH2) of 44 weight %.
The result who in " MTO+OC " hurdle, provides represent based on live catalyst is provided in embodiment 7 and embodiment 5 the result produced adds and catalyst performance.
In the embodiment of table 2 5+7, this hurdle result is called from the CH2 of MeOH with from the left-hand column sum of the CH2 of OC.From the CH2 hurdle of MeOH be left side embodiment 7 hurdles 80.2% and be 19.8% of left side embodiment 6 hurdles from the CH2 hurdle of OC.Two reaction zones of this proof are with respect to the advantage of the reactor of embodiment 6.
Embodiment 8-contrast (using the OC test of blended material, 30%C4-C5 recirculation)
10ml in the tubular reactor that is loaded into internal diameter 11mm (6.2g) catalyzer C particle (35-45 order) is carried out catalyst test.Make contain 70 weight %MeOH and 20 weight % non-annularity C4 hydrocarbon (63% alkene) and 10 weight % basically the raw material of non-cyclic olefin C5 (59% alkene) in fixed-bed reactor at 550 ℃, WHSV=3.7h
-1, carry out catalytic cracking under the P=1.5 crust absolute pressure.
The result of the average catalyst performance between on-stream period in initial 5 hours is in table 3.Described value is the weight % on alkene (CH2) basis.
The result that table provides among the 2-3 shows: higher aromatic hydrocarbons (aromatics) content and lower C3-/C2-ratio under the situation of alkene C4-C5 recirculation being returned in the MTO reactor provide higher alkene loss and lower potentially total productivity of propylene in described process.On the contrary, in two reaction zones that separate, react the productive rate maximization of allowing each process of optimization and making propylene.
Claims (21)
1. by the method for the organic raw material that contains oxygen, halide or sulfur-bearing, comprising with the XTO-OC method manufacturing light olefin of combination:
A0) provide the described organic raw material that contains oxygen, halide or sulfur-bearing of first part and second section;
A) provide the catalyzer that comprises zeolite molecular sieve, described zeolite molecular sieve contains at least 10 yuan of annular distance openings or bigger hole opening in its microvoid structure;
B) provide XTO reaction zone, OC reaction zone and catalyst regeneration zones, described catalyzer circulates in described three districts, feasible at least a portion through the regenerated catalyzer passes to described OC reaction zone, and at least a portion that at least a portion of the catalyzer in the described OC reaction zone passes to the catalyzer in described XTO reaction zone and the described XTO reaction zone passes to described breeding blanket;
C) make the described organic raw material that contains oxygen, halide or sulfur-bearing of described first part in described XTO reactor, under the condition of at least a portion that transforms described raw material effectively, contact the XTO reactor effluent that comprises light olefin and heavy hydrocarbon fractions with formation with described catalyzer;
D) described light olefin is separated with described heavy hydrocarbon fractions;
E) the described organic raw material that contains oxygen, halide or sulfur-bearing that makes described heavy hydrocarbon fractions and described second section contacts under the condition that effectively described heavy hydrocarbon fractions and at least a portion of containing the organic raw material of oxygen, halide or sulfur-bearing is converted into light olefin with described catalyzer in described OC reactor.
2. the process of claim 1 wherein that the amount of " X " of the described second section in the OC raw material makes described OC reactor work near the boundary of heat absorption and heat release condition.
3. the method for claim 2, wherein the ratio of " X " of the described second section in the OC raw material is about 15～about 30 weight %.
4. the process of claim 1 wherein that described catalyzer is the P-modified zeolite.
5. the method for claim 4, wherein said P-modified zeolite is by comprising the method manufacturing of following order:
-at the H of MFI, MEL, FER, MOR, clinoptilolite
+Or NH
4 +Select zeolite (advantageously have 4～500 Si/Al than) in the form;
-introduce P introducing effectively under the condition of at least 0.05 weight %P advantageously;
If-there is liquid, with solid and liquid separation;
-optional washing step, perhaps Ren Xuan drying step, perhaps Ren Xuan drying step and washing step afterwards;
-calcining step.
6. the method for claim 4, wherein said phosphorus-modified zeolite is by comprising the method manufacturing of following order:
-at the H of MFI, MEL, FER, MOR, clinoptilolite
+Or NH
4 +Select zeolite (advantageously having 4～500 Si/Al ratio, is 4～30) in the form in embodiment;
-decatize 0.01～200 hour under 400～870 ℃ temperature;
-under the condition of from described zeolite, removing signal portion Al effectively, leach with aqueous acid solution;
-use the aqueous solution that contains the P source to introduce P introducing effectively under the condition of at least 0.05 weight %P advantageously;
-with solid and liquid separation;
-optional washing step, or optional drying step, or optional drying step and washing step afterwards;
-calcining step.
7. the process of claim 1 wherein that described catalyzer is the catalyst complex of making by the method that comprises the steps:
A) select to have the molecular sieve in the hole of 10 yuan or more polynary ring
B) described molecular sieve is contacted with the metal silicate that comprises at least a alkaline-earth metal, make described mixture comprise the silicate of at least 0.1 weight %.
8. the process of claim 1 wherein that described catalyzer is the alkaline-earth metal made by the method that comprises the steps or the molecular sieve (M-P-modified molecular screen) of rare earth metal P-modification:
A) select at least a molecular sieve, described molecular screening is from one of following:
-contain the P-modified molecular screen of at least 0.3 weight %P
-before the step b) or during introduce the molecular sieve of at least 0.3 weight %P with the P modification
B) described molecular sieve is contacted to introduce described alkaline-earth metal or the rare earth metal M of 0.05 weight % at least with the compound (compound that contains M) of alkaline including earth metal or rare earth metal.
9. each method in the aforementioned claim, wherein will be from all catalyst transport of described revivifier to described OC reaction zone, further be delivered to then described XTO reaction zone and at last with all catalyst transport of described XTO reaction zone to described revivifier (described breeding blanket).
10. the method for claim 1～8, wherein will be from all catalyst transport of described revivifier to described OC reaction zone, further be delivered to described XTO reaction zone then and at last the part of the catalyzer of described XTO reaction zone be delivered to described revivifier (described breeding blanket) and other parts are delivered to described OC reaction zone.
11. the method for claim 1～8, wherein will be from all catalyst transport of described revivifier to described OC reaction zone, the part of the catalyzer of described OC reaction zone further is delivered to described XTO reaction zone and other parts are delivered to described revivifier (described breeding blanket) and will be from all catalyst transport of described XTO to described OC reaction zone.
12. each method in the aforementioned claim wherein is delivered to described OC reactor effluent segregation section and reclaims described light olefin; With at least a portion of the hydrocarbon that will have 4 or more a plurality of carbon atoms in the recirculation of the ingress of described OC reactor, it randomly mixes with the hydrocarbon with 4 or more a plurality of carbon atoms that reclaims from the effluent of described XTO reactor.
13. the method for claim 12, wherein, with described hydrocarbon with 4 or more a plurality of carbon atoms before the recirculation of the ingress of described OC reactor, described hydrocarbon with 4 or more a plurality of carbon atoms is delivered to the after-fractionating device to remove heavy component.
14. each method in the claim 1～11 is wherein mixed described OC reactor effluent and described XTO reactor effluent and is delivered to fractionator, perhaps delivers to same fractionator, and reclaims described light olefin; At least a portion of hydrocarbon that will have 4 or more a plurality of carbon atoms is in the recirculation of the ingress of described OC reactor.
15. the method for claim 14, wherein, with described hydrocarbon with 4 or more a plurality of carbon atoms before the recirculation of the ingress of described OC reactor, described hydrocarbon with 4 or more a plurality of carbon atoms is delivered to the after-fractionating device to remove heavy component.
16. each method in the aforementioned claim, wherein, ethene is in whole or in part in the recirculation of described OC reactor; Described ethene can be from the segregation section of described XTO reactor or from the segregation section of described OC reactor or from the segregation section of the segregation section of described XTO reactor and described OC reactor or even from optional shared recovery zone.
17. each method in the aforementioned claim, wherein, ethene is in whole or in part in the recirculation of described XTO reactor; Described ethene can be from the segregation section of described XTO reactor or from the segregation section of described OC reactor or from the segregation section of the segregation section of described XTO reactor and described OC reactor or even from optional shared recovery zone.
18. each method in the aforementioned claim, wherein the paraffinicity in the raw material of the ingress of described OC reactor is at least 20 weight % on the carbon back plinth.
19. each method in the aforementioned claim, wherein make ethene further randomly with one or more comonomer polymerizations.
20. each method in the aforementioned claim, wherein make propylene further randomly with one or more comonomer polymerizations.
21. each method in the aforementioned claim wherein must contain at least 0.1% carbon from described OC district and the catalyzer that flows to described XTO section.
Applications Claiming Priority (7)
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| EP08158924.4 | 2008-06-25 | ||
| EP08158924A EP2143700A1 (en) | 2008-06-25 | 2008-06-25 | Process to make olefins from oxygenates |
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| EP09154232.4 | 2009-03-03 | ||
| PCT/EP2009/057888 WO2009156434A2 (en) | 2008-06-25 | 2009-06-24 | Process to make olefins from organics |
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| CN102076636B CN102076636B (en) | 2014-04-16 |
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| EP (1) | EP2300396B1 (en) |
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| CN104582842A (en) * | 2012-07-03 | 2015-04-29 | 国际壳牌研究有限公司 | Process for preparing ethylene and/or propylene |
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| CN102464535B (en) * | 2010-11-17 | 2014-03-26 | 中国石油化工股份有限公司 | Method for producing low carbon olefin from methanol or dimethyl ether |
| DE102011013911A1 (en) * | 2011-03-15 | 2012-09-20 | Süd-Chemie AG | Improved process for the preparation of a zeolite based catalyst for the conversion of methanol to olefins |
| DE102011013908A1 (en) * | 2011-03-15 | 2012-09-20 | Süd-Chemie AG | Modified catalyst for the conversion of oxygenates to olefins |
| DE102011013909A1 (en) * | 2011-03-15 | 2012-09-20 | Süd-Chemie AG | Process for the preparation of a zeolite based catalyst for the conversion of methanol to olefins |
| US9931619B2 (en) * | 2013-04-18 | 2018-04-03 | Lotte Chemical Corporation | Ethanol dehydration catalyst for energy saving and method of manufacturing ethylene using same |
| EP3078651B1 (en) | 2013-12-03 | 2019-01-02 | Dalian Institute Of Chemical Physics Chinese Academy of Sciences | Method for preparing a light olefin using an oxygen-containing compound |
| EP3078652B1 (en) | 2013-12-03 | 2018-07-18 | Dalian Institute Of Chemical Physics, Chinese Academy of Sciences | Method for preparing a light olefin using an oxygen-containing compound |
| US10293333B2 (en) * | 2013-12-20 | 2019-05-21 | Clariant Produkte (Deutschland) Gmbh | Catalyst containing phosphorus for converting oxygenates into olefins |
| FR3061037B1 (en) * | 2016-12-23 | 2021-07-02 | Ifp Energies Now | SOLID OXYGEN CARRIER BASED ON TECTOSILICATES, ITS PREPARATION PROCESS AND ITS USE FOR A CHEMICAL LOOP OXIDO-REDUCTION PROCESS |
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| EP0568913A2 (en) * | 1992-05-03 | 1993-11-10 | Dalian Institute Of Chemical Physics | Process for the conversion of methanol to light olefins and catalyst used for such process |
| US6303839B1 (en) * | 2000-06-14 | 2001-10-16 | Uop Llc | Process for producing polymer grade olefins |
| CN1803738A (en) * | 2005-01-14 | 2006-07-19 | 环球油品公司 | Conversion of oxygenate to propylene using moving bed technology and a separate heavy olefin interconversion step |
| WO2009016155A2 (en) * | 2007-07-31 | 2009-02-05 | Total Petrochemicals Research Feluy | Use of phosphorus modified molecular sieves in conversion of organics to olefins |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104582842A (en) * | 2012-07-03 | 2015-04-29 | 国际壳牌研究有限公司 | Process for preparing ethylene and/or propylene |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2300396B1 (en) | 2019-08-07 |
| EP2300396A2 (en) | 2011-03-30 |
| WO2009156434A2 (en) | 2009-12-30 |
| EA021226B1 (en) | 2015-05-29 |
| EA201170084A1 (en) | 2011-06-30 |
| US8957272B2 (en) | 2015-02-17 |
| WO2009156434A3 (en) | 2010-02-18 |
| CN102076636B (en) | 2014-04-16 |
| US20150152020A1 (en) | 2015-06-04 |
| US9561990B2 (en) | 2017-02-07 |
| US20110152479A1 (en) | 2011-06-23 |
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